Marker and method of its making

FIELD: polymeric industry.

SUBSTANCE: marker comprises substrate provided with organic polymeric surface, coating solidified by irradiation and applied on the organic polymeric surface, and coloring agent applied on the solidified coating. The substrate has light-reflecting layer. The coloring agent can not be removed by five-fold wiping the surface with petrol. The method comprises preparing the substrate and applying the coloring agent on the coating solidified by radiation. The substrate has light-reflecting layer.

EFFECT: prolonged service life.

28 cl, 6 dwg, 2 tbl

 

Polymer coatings are widely used for the manufacture of marking products with light-reflecting properties. The product has reflective properties, if it is able to reflect a substantial portion of incident light in the direction of the light source. Retroreflective properties of the products provide improved visibility in poor or low light conditions and in situations where it is necessary to consider from a great distance.

Polymer coatings are also used for the manufacture of marking products with enhanced durability. Increased durability of marking products can be important in situations where marking the product may be exposed to corrosive fumes, ultraviolet radiation, high temperature or humidity, etc. In some cases, an important aspect of durability of the product is resistant to abrasion and to the cleaners or solvents included in the cleaning solutions. If you do not want to achieve a high durability of the products (for example, labels for returnable package), you can use a cheaper coverage with a short lifetime.

Polymer coatings are also used for the manufacture of marking products that bear the alphanumeric information, a bar code or the picture is K. Often marking articles carry the information that is repeated or monotonically increasing on a large number of such products, for example, be applied labels for automobile license plates can contain the same information about the state or County that is repeated in a large number of identification labels.

For many years, identification labels for vehicles used to confirm the fact of payment of applicable taxes and/or completing the required inspection procedures and registration. It is generally accepted that small affect identification labels, colloquially called "stickers" (usually about the size of 2.5 to 3.8 cm (1 to 1.5 inches) or so) is placed at a certain place of the license plate of the vehicle as evidence of payment of the annual tax and registration fee. Similar examples can serve stickers used as evidence satisfactory results of testing the car for safety or as evidence satisfactory results of testing the exhaust emissions of the vehicle or for information on his insurance.

Such items as identification labels currently are made by printing information on the surface of the retroreflective material such methods is how, for example, high, offset or bitmap printing, etc. which, as a rule, are not suitable for printing small runs. These methods usually provide satisfactory print quality, readability and adhesion, but the equipment for the implementation of these processes may be relatively expensive. In addition, when using high or offset printing is necessary in advance to produce print matrix or rubber offset plate, and when using screen printing need to produce a raster. The production matrix, offset plates or raster can be an expensive and lengthy process. In addition, in many cases, are dissolved dyes, which creates the problem of environmentally sound disposal of the solvent. In the known processes may require the use of drying ovens and additional time for drying. In addition, known methods of printing information on labels have restrictions on the possibility (or lack thereof) simply changing the information that is printed on separate instances of labels.

When laser printers, using the method of Electrophotography, fell, they began to be applied for online (on demand) printing in small batches. For example, it would be desirable that identification labels or other mA is Kirochnaya products using a polymer coating, can quickly be printed in small batches.

However, unfortunately, the usual combination of compositions of polymeric coatings and pigments, such as that used at high or screen printing, as a rule, not compatible to provide the necessary adhesion, transparency, and durability under conditions of high temperature or exposure to abrasive or chemical substances (e.g. petrol). In other words, colorants, for example, toners, are not always sufficiently well stick to the core material, and formed by these substances, the image can be easily removed. This is a significant problem for identification labels, which can often come in contact with the active chemical substances as gasoline.

There are many methods of improving the adhesion of the pigments to the sheet material coatings. For example, to improve the adhesion of the coloring matter applied to the retroreflective material as the uppermost layer of material used substances such as polyvinyl chloride, cross-linked polyurethane and a composition consisting of polyethylene terephthalate and copolymers of vinylidenechloride. As the upper layer is also used halogen-free acrylourethane, ogruntovannye to improve the adhesion of the coloring matter, diluted aqueous acrylate polymer or adhesive or cured by corona discharge. To protect the underlying layers is applied also drawing on the printed image as a transparent coating of aliphatic or aromatic polyurethane or acrylate polymers, or extruded thermoplastic coating film of aliphatic polyurethanes, copolymers of ethylene or propylene homopolymers or ethylene or propylene. However, many of these options do not provide the necessary durability required in some applications, in particular for identification labels, which can often come in contact with the active chemical substances as gasoline.

The present invention relates to marking devices, and methods for their manufacture, in which the surface marking of the products has improved adhesion with respect to dye substances. Such marking products include a substrate having a surface not containing cellulose organic polymer, the cured radiation coating on the surface not containing cellulose organic polymer, and applied the coloring matter (which creates an image in the form of characters, numbers, etc).

The present invention is a marking product include what it is in itself a substrate, consisting of not containing cellulose organic polymer; the cured radiation coating (preferably cured by electron beam or ultraviolet radiation, and more preferably, ultraviolet radiation), deposited on a given surface of not containing cellulose organic polymer; and printed at the specified utverjdenie radiation coating of coloring matter, despite the fact that the dye is not removed in significant ways in the five cycles (preferably, after 10 cycles, and most preferably, in the 25 cycles) wiping coloring substance gasoline. Preferably, the substrate is a reflective material which, preferably, is part of the certification label.

The dye preferably consists of a dye and a binder which is a polymer selected from the group comprising polyesters, polyvinyl, polyolefin, acetyl-polyvinyl, alkyl - or aryl-substituted acrylate or methacrylate, copolymers of ethylene or propylene with acrylic acid, methacrylic acid or vinyl acetate, and mixtures thereof. Preferably, the radiation curable coating is made from allow the curing ultraviolet radiation compositions, which include South Africa is at, preferably aliphatic acrylourethane.

In preferred embodiments of the present invention the dye is not removed substantially in the 1000 cycles mechanical abrasion, or by pressing a pressure-sensitive adhesive tape to otverzhdennom radiation coverage under the pressure of the thumb and remove the tape. In preferred embodiments of the present invention utverjdenie radiation coating also is not removed substantially in the pressing pressure-sensitive adhesive tape to otverzhdennom radiation coverage under the pressure of the thumb and remove the tape.

In preferred embodiments of the present invention utverjdenie radiation coating, which may be uniform or forming a figure, also is not removed in significant ways in the five cycles of rubbing the cured radiation coverage gasoline or as a result of 1,000 cycles mechanical abrasion of the cured radiation coverage.

In some preferred embodiments of the present invention the marking device does not have a protective coating on top of the coloring matter.

The present invention also represents a marking device, including: retroreflective sheet material with the surface of the polymer content of inorganic fillers; utverjdenie radiation coating consisting of aliphatic acrylourethane deposited on the surface of the organic polymer; and dye deposited on utverjdenie radiation coating, despite the fact that the dye is not removed in significant ways from marking products in the five cycles of wiping coloring substance gasoline.

In another embodiment of the present invention the marking device includes retroreflective sheet material with the surface of the organic polymer; the cured radiation coating consisting of aliphatic acrylourethane deposited on the surface of the organic polymer; and the coloring matter deposited on utverjdenie radiation coverage.

The present invention also provides a method of manufacturing marking products, which consists in preparing a substrate having a surface not containing cellulose organic polymer (preferably, the retroreflective sheet material; applying the cured radiation coating (preferably selected from the handle UV compositions); and applying utverjdenie radiation coating of coloring matter by using a technology selected from the group comprising: an electrostatic printing, the directional deposition of ions, magnetic tape printing, inkjet (ink) printing, letterpress, offset (e.g., offset press printing and gravure printing. Preferably, in this method, the dye had moved on significantly in the five cycles of wiping coloring substance gasoline. In addition, it is preferable that the marking of the product did not have a protective coating applied on top of the coloring matter.

In another embodiment of the present invention presents a manufacturing method of marking articles, which consists in preparing a substrate having a surface not containing cellulose organic polymer (preferably, this surface is formed utverzhdennym radiation coating and, more preferably, the substrate was retroreflective sheet material; and applying the coloring matter on the surface not containing cellulose organic polymer by a method selected from the group comprising electrophotographic printing and gravure printing, despite the fact that the dye is not removed in significant ways in the five cycles of wiping coloring substance gasoline. Preferably, the marking device may not have protective coatings applied on top of the coloring matter.

In another embodiment of the present invention p is edstaven a method of manufacturing a marking products which consists in preparing a substrate having a surface not containing cellulose organic polymer (preferably, this surface is formed utverzhdennym radiation coating and, more preferably, the substrate was light reflective sheet layer; and applying the coloring matter on the surface not containing cellulose organic polymer by a method selected from the group comprising high printing and offset printing, despite the fact that the dye is not removed in significant ways in the five cycles of wiping coloring substance gasoline and, in addition, a marking device does not have a protective coating applied on top of the coloring matter.

In another embodiment of the present invention presents a method of manufacturing types : identification label, which consists in creating the types of label having a surface not containing cellulose organic polymer; and screen printing dye on the surface of not containing cellulose organic polymer, despite the fact that the dye is not removed in significant ways in the five cycles of wiping coloring substance gasoline, and in addition identification label does not have an external protective coating.

Also presented a method of manufacturing marker the adjustment of product which consists in preparing a substrate having a surface not containing cellulose organic polymer coated with utverzhdennym radiation coating; screen printing dye on the surface of the cured radiation coverage, despite the fact that the dye is not removed in significant ways in the five cycles of wiping coloring substance gasoline and, in addition, a marking device does not have an external protective coating.

Another method of manufacturing the marking of the product is the preparation of a substrate having a surface not containing cellulose organic polymer coated with utverzhdennym radiation coating; and applying the coloring matter on the surface of the cured radiation coating method of printing by means of thermal transfer, despite the fact that the dye is not removed in significant ways in the five cycles of wiping coloring substance gasoline.

BRIEF DESCRIPTION of DRAWINGS

Hereinafter the invention is explained by using the drawings, in which:

figure 1 is a view in plan on an obverse surface identification label according to the present invention;

figure 2 - cross section of a label in accordance with Fig. 1, located on the temporary carrier;

figure 3 - schematic cross-section Svetofor the replacement of sheet material, having a sublayer for printing layer according to the present invention;

4 is a cross-section of the marking of the product according to the present invention;

5 is a view of the front surface marking of the product according to the present invention;

6 is a view of the front surface of the identification label according to the present invention.

In the following description uses as an example the identification label. However, the present invention covers other marking products, such as labels for use indoors or outdoors, labels for product identification, inventory labels and control stamps, stickers and window stickers indicating the inspection of vehicles and other equipment, Parking permits, stickers indicating the duration, speed limit signs, signs with street names, license plates, as well as other road signs and markings road markings, and methods for their manufacture.

Example of identification label 10 according to the present invention shown in figures 1 and 2. Identification label 10 includes a sheet material 12 having a first major surface 14 and second major surface 16. In the shown implementation on the second surface 16 of the applied adhesive layer 17. The sheet material 12 has a hidden protective hole 18 is, 18b, which specify the location of the tear or rupture of the sheet, thus providing a "fragile" labels. In some cases, before use, the label 10 may be detachable protective substrate (for example, the temporary carrier 20. The substrate 20, to which the label 10 is attached with the possibility of separation, can be used to facilitate the manufacture of the label and use them. If anything, there may be used a substrate (not shown)attached with the possibility of branching to the first main surface 14 - one or in combination with the substrate on the second main surface 16.

The first main surface 14 adapted to accommodate readable information (i.e. marking) by applying the coloring matter (e.g., toner or ink). In most cases, information in the form of alphanumeric characters or other symbols such as barcodes, logos, etc. of desired colour should be read with the naked eye. If necessary, information may allow reading by other means, for example, contain automatically read the infrared image. Those familiar with this area, can easily indicate the many appropriate ways to create the desired image on the main surface 14. To improve visibility and/or accessibility certification label preferably, the entire surface 14, or at least its part b is La reflective.

Typically, the surface 14 is a surface not containing cellulose organic polymer, which can be directly applied (not shown) of coloring matter.

Preferably, the organic polymer surface contains utverjdenie radiation substance, although it is possible to use other substances for creating surface with improved adhesion. Alternatively, before applying the dye to the sheet material 12 on a specified surface not containing cellulose organic polymer can be coated, forming a special sublayer for printing (not shown) with improved adhesive properties of the surface. Such a sublayer for printing may have a different thickness from about 0.0001 to about 0.0015 inches (from about 2.5 microns to about 38 microns). As the only substrate for printing it can work with minimal thickness, but, by increasing its thickness, may increase the resistance of the polymer surface and underneath materials (e.g., reflective layer) to the effects of weather conditions. It is essential that such a coating, which is preferably utverzhdennym radiation coating, creates a very receptive to dye substances to the surface, so you may the be to pick a combination of pigments to obtain the desired properties. Materials suitable for the manufacture of substrate for printing is described below.

The second major surface 16 adapted for insertion of the label 10 to the substrate (not shown). In some cases, as shown in Fig. 2, the surface 16 may be covered with an adhesive layer 17. The choice of adhesive may depend, in particular, on the characteristics of other parts of the label 10, the characteristics of the substrate to which the label 10 stick, from the way and conditions in which the label should be applied, and from impacts, which will be subject to the label and the substrate during operation. Examples of adhesives suitable for different implementations of the present invention can serve as adhesives, pressure-sensitive, adhesive, rasplavljajutsja when heated and activated adhesive (for example, a substance that is activated by radiation or chemical initiators). Familiar with this area can easily choose an adhesive that is suitable for a particular embodiment of the present invention.

In other embodiments of the present invention, the label 10 is attached to the substrate with adhesive pre-applied to the surface of the substrate. In such cases, the surface 16 may initially be suitable for use with known adhesive or may be specially is prepared using a suitable exposure to plasma or corona discharge or primed with a special coating, improving its compatibility with known adhesive. Familiar with this area can easily choose a suitable adhesive substances and processing methods. For "fragile" marking products, such as identification labels, it is preferable to use adhesives which the peeling from the substrate efforts greater than the adhesion between other layers of the product. In this scenario, when you try to detach the product from the substrate it is "fragile" (e.g., torn or distorted). Typically, such adhesives used a pressure-sensitive adhesive, for example, known pressure-sensitive adhesive based itachinaruto and acrylic acid.

In Fig. 3 shows the preferred performance retroreflective polymeric sheet material 80 according to the present invention. Sheet material 80 is composed of the base layer, which includes a separate reflective elements 62 and sublayer for printing 82, and remove the protective coating 24, which is used as the bottom layer. Retroreflective element 62 consists of a pressure-sensitive adhesive 36, the monolayer of microspheres 30, deposited on a reflective substrate 32, the spacer cover 43 and the fastening layer 44.

Sheet material 80 with a sublayer for printing 82 is rednaznachen for direct application of dyes, consisting of a dye and a binder (for example, dye/binder resin). In addition, the underlayer for printing 82 participates in the creation of other functional properties of the polymer layer according to the present invention. In the retroreflective material 80 sublayer 82 may serve as a protective and/or antireflective coating. Layer 82 may also complement the ratio of optical properties needed to provide retroreflective properties.

The base layer of sheet material 80 includes retroreflective elements 62 and the protective coating 24. However, in some cases, the base layer can contain only elements 62, for example, if the sheet material 80 is glued to the substrate. In other variants, including the following embodiments, a coating similar to the coating 24 may be an additional part of the base layer.

One implementation of marking products with printed labeling is shown schematically in cross section in Fig. 4 and the whole figure 5. Marking the product contains 120 marks 122 and the base layer comprising retroreflective polymeric material 62, as described above. Marking 122 may be formed by a dye/binder resin, and a sublayer for printing 82 may be formed, for example, compositions based on Oteri emeu radiation resin. Sublayer for printing may be applied uniformly or in a pattern. Optionally it may also contain dye.

A General view of another implementation of marking products shown in Fig.6. Article 130, in this case, the identification label includes marking 132 and retroreflective polymeric material similar to the sheet material 80 shown in figure 3. Marking 132 may be formed by a dye/binder resin.

If necessary, the product in accordance with the present invention may have a protective coating to improve durability. Such a protective cover should be placed over the applied coloring matter. In a preferred execution of the protective layer is not necessary, because in accordance with the present invention the dye forming the marks and the composition forms a surface with improved adhesion, are selected to provide the desired durability without the need to "bury" the markings inside the marking of the product. If necessary, the covering layer may be adhesive.

Retroreflective polymeric sheeting material in preferred implementations of the products according to the present invention can be, for example, "bugles" - in the form of a sheet material containing layer encapsulated lens (see, n is the sample, U.S. patent No. 3.190.178, 4.025.159, 4.896.943, 5.064.272 and 5.066.098), or in the form of a sheet material containing layer stacked lenses (see, for example, U.S. patent No. 2.407.680), or in the form of a sheet material containing a layer of cubic reflecting elements (see, for example, U.S. patent No. 3.684.348, 4.801.193, 4.895.428 and 4.938.563).

For example, in one of the embodiments of the present invention the core layer may include the upper bonding layer; a protective layer consisting, for example, of polyvinyl butyral; located under the fastening layer is a monolayer of microspheres having upper and lower surfaces and the bottom surface embedded in a protective layer, and the upper surface embedded in the bonding layer; a reflective layer placed under the monolayer of microspheres, and the bottom layer of pressure-sensitive adhesives. Bonding layer may consist of, for example, of polyvinyl butyral or synthetic polyester resins, cross-linked bonds with the resin of butyl-melamine. The thickness of the binding layer typically lies between 20 microns and 120 microns. Microspheres are usually made of glass with a refractive index between 2.1 and 2.3, and have a diameter of from about 30 microns to about 200 microns, preferably with an average diameter of about 60 microns. Typically, microspheres at 50% immersed in the bonding layer. Protective is Loy usually has such a thickness, he is separated from the outer surface of the microspheres at a distance of about a quarter of the average diameter of the microspheres. As the reflective material can be used a layer of metallic flakes or deposited by evaporation in vacuum or by chemical metal layer, for example, aluminum or silver.

One way of forming a substrate for printing as an integral part of the polymeric sheet material includes the steps: a) preparing a polymer layer, preferably the base layer with light reflecting elements; (b) application suitable for curing the radiation of the composition to the specified polymer layer; and (C) curing the specified composition with radiation to create a polymeric material having a sublayer for printing. Preferred compositions to create a substrate for printing can be applied using a variety of known technologies including, for example, dipping, spraying, application flow, drawing the veil, application roller, spread through placket, spread with a knife, spread with the help of coiled wire and gravure printing. Familiar with this area can easily choose for a particular application one of these or other suitable methods of application. After coating on a polymeric material composition is usually preferably exposed from the teachings to create a polymeric material with the upper exposed surface, representing a sublayer for printing.

Compositions in accordance with the present invention have the advantage that they allow designing polymeric sheet material consisting of a single layer, which not only provides functional specifications for the implementation of which previously required multiple layers, such as an external coating, antireflection layer, and the like, but also suitable for direct printing using the dye/binder-based resins. Thus, the method of manufacturing according to the present invention allows to significantly simplify the design of sheet material.

Identification labels are just one of the examples of the marking of products covered by the present invention. Surface material with improved adhesion, which preferably is utverzhdennym radiation material, and more preferably, a pronounced sublayer for printing, utverzhdennym a certain type of radiation, and the dye are chosen in such a way that the marking product had one or more useful property from among the following: (1) abrasion resistance; (2) good adhesion between the various layers of the product or between the marking of the sublayer for printing; (3) resistance to solvents, in particular, resistance to gasoline; (4) suitability for printing; and (5) resistance to the environment. The term "resistance to environmental exposure" refers to such characteristics of the product, as the stability of the brightness of the return light, resistance to contamination and/or resistance to yellowing under normal operating conditions outdoors where sunlight, temperature or other environmental parameters can affect the properties of materials. Preferably, these properties could be achieved without the need for applying a protective material on top of the coloring matter (i.e. without using the protective layer).

Described below in the "Examples" section test methods can be used to determine whether the product according to the present invention one or more of the above properties. Typically, the surface with improved adhesion (preferably, a sublayer for printing and, more preferably, utverjdenie radiation coating and coloring agents can be tested separately.

As a rule, under the same test conditions after carrying out one or more of the following test procedures were removed less coloring matter, compared with the amount of coloring matter, delavcev is the same, but not having sublayer for printing products.

The dye is preferably not removed significantly after conducting one or more described in the "Examples" section of the test procedures. This means that the result of carrying out the required tests were removed not more than about 50% (preferably, less than about 25%, and more preferably, less than about 10%) of the coloring matter. The number of remote coloring matter may be assessed qualitatively. Alternatively, it can be quantified, measured by the densitometer, the density of the image before and after each test.

The effect of test procedures on a surface with improved adhesion can be measured both qualitatively and quantitatively. For example, for each tested substrate for printing the number of the remote with his material can be determined qualitatively or quantitatively. Preferably, the underlayer for printing should not significantly removed as a result of one or more test procedures described in the "Examples"section. Here it means that the result of carrying out the required tests are removed not more than 50%, preferably not more than 25%, and more preferably, not more than 10% of the material substrate for printing. If the sublayer for printing on the Rushen, the amount removed of the material can be determined by measuring the densitometer, the density of its color before and after each test. Another way to determine the degree of impact test procedures on a surface with improved adhesion is measured by the respective device [gloss meter] value loss of gloss after the necessary tests.

For example, it is preferable that the dye (or only the sublayer for printing) had moved on significantly in the 5 cycles, preferably 10 cycles, and even more preferably 25 cycles of wiping the coloring matter (or only substrate for printing) gasoline. Preferably, the dye (or only the sublayer for printing) had moved on significantly in the 1000 cycles mechanical wiping the coloring matter (or only substrate for printing). Preferably, the dye (or only the sublayer for printing) was not removed substantially in the pressing force of the thumb to kasashima substance (or only to the sublayer for printing) tape coated with pressure-sensitive adhesive substance, and its subsequent removal.

Surface with improved adhesion

The surface 14 (1) may be a surface not containing cellulose org is practical polymer, directly to which is applied the dye, or it may be coated with a different polymer material (i.e. sublayer for printing), which improves the adhesion to the dye substances. Preferably, this material is a material suitable for processing radiation. Unexpectedly it was found that the cured radiation materials are susceptible to a variety of coloring substances, caused by very different methods of printing. Usually this material is an oligomer or polymer. It can be made from the original substance, which should be applied in a sufficiently fluid state to allow to form a coating, and then to harden, forming a film. In another embodiment, it can be applied in the form of pre-prepared films. Curing can be achieved by chemical means (i.e. by polymerization or crosslinking) and/or drying (i.e. removal of solvent) or simply by cooling. The original substance of the coating may be an organic composition that is dissolved in water or another solvent or 100% dry (i.e. containing no solvent). I.e. organic polymeric surface according to the present invention can be formed from 100% solid composition or covered by its solution (e.g., ketone, tetrahydro the uranium or in water), followed by drying and/or curing. The original substance of the coating preferably is a 100% dry composition containing no solvent (i.e., not more than 1% by weight). This means that the original substance is present no more than about 1% (by weight) not participating in the reaction diluent (as defined below). In accordance with this starting material forms a coating or as a result of simple drying or its components polymerize or form cross-links by any of a variety of curing mechanisms (e.g. oxidative curing by oxygen, heat curing, curing under the influence of moisture or radiation with high energy, condensation polymerization, polymerization under the action of admixtures or combinations of these mechanisms).

The preferred starting material of the coating is able to irreversibly turn into a solid oligomeric/polymeric material is sometimes referred to as "reactivities substance". Here, the term "reactivities substance" will be used to specify reactive systems, irreversibly cured by heating under the influence of energetic radiation such as electron beam, ultraviolet or visible light and the like, or with time upon the addition of a chemical catalyst, moisture, etc. the Term "reactions osoby" indicates what components of the initial substances enter into the polymerization reaction or cross-linking (or both simultaneously) to each other (or themselves) by using any of the above mechanisms.

Components selected for inclusion in the composition of the starting substances of the coating, can be used to improve the durability of the product, for example, reflective layer identification label to the effects of the environment. Depending on the design of sheet material lying below the coating surface can preferably interact with the various components of the original substance (for example, if the design included utverjdenie radiation coverage of the underlying organic polymer material). The term "interaction" refers to a wide range of interaction mechanisms, such as the violation of the smoothness of the surface, dissolution or mutual penetration. It is also possible covalent interaction (e.g., polymerization or crosslinking) between the original substance of the coating and the underlying surface.

The original substance of the coating may contain reactive not reactive components. Not reactive source materials usually contain polymers or oligomers which are dissolved or dispersed is not reactive volatile liquid, but can also be used 100% of the dry composition. Such compositions may consist, for example, deposited from a solvent thermosetting, or from a substance, raspravlyayuschegosya when heated, or deposited from the water of the latex. Although not reactive source materials coatings can be used, they are not preferred.

Suitable for formation of surfaces with improved adhesion preferably are used as starting substances coatings containing reactive components, i.e. substances capable of polymerization or to form cross-links using a variety of mechanisms (e.g. oxidative curing, condensation, solidification under the influence of moisture, radiation or thermal curing of free-radical systems, etc. or a combination of such mechanisms). In the list of examples includes, without limiting it to such amine (i.e. aminoplasts) resin as the alkylated wreath-formaldehyde resins, melamine-formaldehyde resins and alkylated, benzoguanamine-formaldehyde resins; acrylate (i.e. acrylate and methacrylate) resin as vinylacetate, calironia epoxy resin, calironia urethanes, calironia acrylates, calironia polyesters, calironia oil and calironia Seeley the ons; such alkyd resins as uretonimine resin, polyester resin, reactive urethane resins; phenol-formaldehyde (i.e. phenol) resin as the resin type, the audio record and novolak (brand identification), phenylacetone resin; epoxy resin as bisphenola epoxy resin; isocyanate; isocyanurate; reactive vinyl resins and the like. In this text, the terms "resin" or "system-based resin" correspond to polydisperse systems containing monomers, oligomers, polymers or combinations thereof.

Such reactive components of the parent substance of the coating can be cured under the action of different mechanisms (for example, by condensation or under the action of impurities) using, for example, thermal or radiant energy, etc. are Particularly preferred form of radiant energy, provides high-speed response (e.g., requiring the application in less than five minutes and, more preferably, less than five seconds). The most desirable to use e-rays due to their ability to penetrate the thick intensely colored coatings, quick and efficient use of energy and facilities management. Other useful types of radiation are ultraviolet light, nuclear radiation, infrared and microwave radiation. In hung is on the specific mechanism of curing, the original substance of the coating may also contain a catalyst, initiator or curing agent, helping to initiate and/or accelerate the polymerization and/or cross-linking.

Among the reactive components of the original substance coating, allowing the curing under the influence of heat and/or over time with the addition of the catalyst includes, for example, such a phenolic resin as the audio record and novolak; such epoxy resin as bisphenol-A-tar; and such amine resin as alkylated ureaformaldehyde resins, melamine-formaldehyde resins and alkylated, benzoguanamine-formaldehyde resin. Depending on the system-based resin, the starting materials for coatings containing components, which themselves are highly reactive and may also contain free-radical thermal initiators, acid catalysts, etc. are examples of free-radical thermal initiators include peroxides such as benzoyl peroxide and azo-compounds. Typically, these components of the initial substances require a curing temperature greater than room temperature (i.e. from about 25°With up to about 30°C), although the known systems are capable of curing at room temperature.

More preferred are the starting substances, the method is passed to cure under the action of radiation. In this text, the terms "curing under the action of radiation and the ability to cure under the action of radiation indicate the curing mechanisms, including polymerization and/or crosslinking in the system based on resin under the influence of visible light, ultraviolet radiation, electron beam, or combinations thereof, possibly in the presence of a suitable catalyst or initiator. There are basically two types of curing mechanism of occurring under the action of radiation - free-radical and cationic curing curing. They usually take place in one stage and use only one of the mechanisms of curing. To combine the useful properties of both systems, you can use a mixture of substances, cured by free-radical and cationic mechanisms. As shown below, it is also possible dual and hybrid curing system.

In cationic systems cationic photoinitiator subjected to ultraviolet radiation, react, decomposing and becoming acidic catalysts. Such acid catalysts support reactions of cross-linking ion mechanism. When the cationic curing of the most widely used epoxy resins, in particular cycloaliphatic epoxy resin, although it is possible application and aromatic epoxides and oligomers based on vinyl ether. In addition, when the cationic curing together with epoxides as transmitting chain agents and means of increasing the elasticity can be applied polyols. Using cationic photoinitiators can cure epoxysilane, as shown Eckberg and others in the UV Cure of Epoxysiloxanes" in Radiation Curing in Polymer Science and Technology: Volume IV. Practical Aspects and Application edited by Fouassier and Rabek, Elsevier Applied Science, NY, Chapter 2, 19-49 (1993). Cationic photoinitiator include salt niewyk cations, such as salts arylsulfonyl, as well as organometallics salt.

Examples of cationic photoinitiators disclosed in U.S. patent No. 4.751.138 (Tumey and others) and No. 4.985.340 (Halazzotti), as well as in European patent applications 306.161 and 306.162. Suitable for epoxysilane photoinitiation is photoactive salt iodine supplied under the trademark UV9310C by GE Silicones, Waterford, NY.

In free-radical systems, the radiation provides a very fast and controlled formation of highly active substances that initiate the polymerization of unsaturated compounds. Examples of substances which can be cured by free radicals include, without limiting it to, acrylate resins, derivatives of aminos with lateral alpha, beta-unsaturated carbonyl groups, derivatives of isocyanurate having at least one unsaturated acrylate side GRU is PU, derivatives isocyanurate having at least one unsaturated acrylate side group, unsaturated polyesters (for example, condensation products of organic diazido and glycols), polential-silicone systems and other ethylene-unsaturated compositions, as well as their mixtures and combinations. Such systems are suitable for curing by radiation, discussed in detail by Allen and others in the "UV and Electron Beam Curable Pre-Polymers and Diluent Monomers: Classification, Preparation and Properties" in Radiation Curing in Polymer Science and Technology: Volume I. Fundamentals and Methods edited by Fouassier and Rabek, Elsevier Applied Science, NY, Chapter 5, 225-262 (1993); Federation Series on Coatings Technology, Radiation Cured Coatings, Federation of Societies for Coating Technology, Philadelphia, PA, pp. 7-13; and Radiation Cured Primer I: Inks. Coatings and Adhesives. RadTech International North America, Northbrook, IL, pp. 45-53 (1990).

Systems that allow curing by free radical mechanism, can be cured using radiation, although they can be cured with the help of thermal energy, if there are sources of free radicals (for example, peroxides or azo-compounds). Therefore, the phrase "capable of curing under the action of radiation and, particularly, the phrase "capable of cure by free-radical mechanism covers systems that can also be cured under the action of thermal energy with the participation of free-radical curing mechanism. On the contrary, the phrase "cured under the influence of radiation" apply is only to those systems, which have been solidified under the influence of radiant (not heat) energy.

The list of acrylate resins suitable for use in accordance with the present invention, includes, but is not limited to, calironia urethanes (i.e. urethaneacrylate), calironia epoxides (i.e. epoxyacrylate), calironia polyesters (i.e. Polyesterimide), calironia acrylics, calironia silicones, calironia polyethers (i.e politically), vinylacetate and calironia oil. Here, the terms "acrylate" and "(functionality)acrylate" equally cover both acrylates and methacrylates, whether it be monomers, oligomers or polymers.

Calironia urethanes are diarylethene simple or polyesters having an NCO group with a hydroxyl end. They are the most preferred. They can be aliphatic or aromatic, but aliphatic calironia urethanes are more preferred because they are less exposed to weather factors. Examples of commercially available accelerandi of urethanes are the products known under the trade names PHOTOMER (e.g., PHOTOMER 6010) company Henkel Corp., Hoboken, NJ; EBECRIL 220 (hecatoncheires aromatic acrylourethane with molecular weight 1000), EBECRIL 284 (diluted 1,6-hexanediamine aliphatic diakrino is tan with a molecular weight of 1000), EBECRIL 4827 (aromatic diacrylate molecular weight 1600), EBECRIL 4830 (diluted tetraethylorthosilicate aliphatic diacrylate molecular weight 1200), EBECRIL 6602 (trifunctionally aromatic acrylourethane with a molecular weight of 1300, diluted trimethyltetradecylammonium) and EBECRIL 8420 (aliphatic diacrylate with molecular weight 1000) company UCB Radcure Inc., Smirna, GA; SARTOMER (for example, SARTOMER 9635, 9645, 963-B80, 966-A80) company Sartomer Co., West Chester, PA; UVITHANE (for example, UVITHANE 782) company Morton International, Chicago, IL.

Calironia epoxides are complex diarylethene bisphenol a epoxy resin. Examples of commercially available accelerandi epoxides are the products known under the trademarks EBECRIL 600 (bisphenol epoxidized with a molecular weight of 525), EBECRIL 629 (apocynaceae with a molecular weight of 550) and EBECRIL 860 (acrylate epoxidizing soybean oil with a molecular weight 1200) company UCB Radcure Inc., Smirna, GA; and PHOTOMER 3016 (bisphenol epoxidized), PHOTOMER 3038 (a mixture of epoxyacrylate with tripropyleneglycol) PHOTOMER 3071 (modified bisphenol a acrylate), etc. of the company Henkei Corp., Hoboken, NJ.

Calironia polyesters are products of the interaction of acrylic acid with complex dibasic acid esters, aliphatic and tiolovymi bases. Examples of commercially available acelerou is the R polyesters are products, known under the trade names PHOTOMER 5007 (hecatoncheires acrylate with a molecular weight of 2000), PHOTOMER 5018 (tetrafunctional acrylate with a molecular weight of 1000) and other calironia polyesters series PHOTOMER 5000 company Henkel Corp., Hoboken, NJ.; and EBECRIL 80 (tetrafunctional modified preferablyat with molecular weight 1000), EBECRIL 450 (modified preferenceactivity fatty acids) and EBECRIL 830 (hecatoncheires preferablyat molecular weight 1200) company UCB Radcure Inc., Smirna, GA.

Calironia acrylates essence of acrylic oligomers or polymers having reactive side or end groups of acrylic acid, capable of forming free radicals involved in subsequent reactions. Examples of commercially available accelerandi acrylates include the products known under the trademarks EBECRIL 745, 754, 767, 1701 and 1755 company UCB Radcure Inc., Smirna, GA.

Calironia silicones, such as silicone, vulcanizing at room temperature, the essence of silicone oligomers or polymers having reactive side or end groups of acrylic acid, capable of forming free radicals involved in subsequent reactions. These and similar acrylates reviewed by Allen and others in the "UV and Electron Beam Curable Pre-Polymers and Diluent Monomers: Classification, Preparation and Properties" in Radiation Curing in Polymer Science and Technology: VolumeI., Fundamentals and Methods edited by Fouassier and Rabek, Elsevier Applied Science, NY, Chapter 5, 225-262 (1993); Federation Series on Coatings Technology, Radiation Cured Coatings, Federation of Societies for Coating Technology, Philadelphia, PA, pp. 7-13 (1986) and in Radiation Cured Primer I: Inks, Coatings and Adhesives, RadTech International North America, Northbrook, IL, pp. 45-53 (1990).

Derivatives isocyanurate having at least one lateral acrylate group, and derivatives of isocyanates having at least one lateral acrylate group, described in detail in U.S. patent No. 4.652.274 (Boetcher and others). Among the examples which resins containing acrylate groups include triacrylate three(hydroxyethyl)isocyanurate.

Aminoplast resin capable of curing by radiation, have oligomer or in each molecule at least one side of the alpha-beta acrylate group. Such unsaturated carbonyl group can be acrylate, methacrylate or acrylamide type. Examples of resins containing acrylamido group include N-(hydroxymethyl)acrylamide, N,N'-occidentalization, ortho - and para-acrylamidophenylboronic phenol, acrylamidophenylboronic phenol novolak, glycolytically, acrylamidophenylboronic phenol, and combinations thereof. Such materials are described in detail in U.S. patent No. 4.903.440 (Larson and others), No. 5.055.113 (Larson and others) and No. 5.236.472 (Kirk and others).

Other suitable unsaturated ethylene resins include mono is Ernie, oligomeric and polymeric compounds, typically containing ether groups, amide groups and acrylate groups. Such unsaturated ethylene compounds preferably have a molecular weight of not more than about 4000. Preferably they are esters resulting from the reaction in the compound containing aliphatic, monohydroxy group or the aliphatic polyhydroxy groups and such unsaturated carboxylate as acrylic acid, methacrylic acid, taconova acid, maleic acid and the like. In this text, the representative examples of acrylate resins are found everywhere. Other unsaturated ethylene resins include monoallyl, polyallyl, polymetallic - esters and amides, carboxylate acids, such as diallylphthalate, dellilachip and N,N-diallyldimethyl and stiren, divinylbenzene and vinyltoluene. It also includes Tris(2-acryloyloxy)isocyanurate, 1,3,5-three(2-methylacetoacetyl)-s-triazine, acrylamide, methylacrylamide, N-methylacrylamide, N,N-dimethylacrylamide, N-vinyl pyrrolidone, N-vinylcaprolactam and N-vinylpyridine.

In containing resin dual curing systems, polymerization or crosslinking occur in two separate stages, involving either the same or different mechanisms. In containing resin hybrid Oteri audacia systems both polymerization or cross-linking act simultaneously under the influence of ultraviolet or electron radiation. Chemical curing mechanisms that may act in this case, include, but are not limited to, radical polymerization of acrylic double ties, radical polymerization of unsaturated polyesters of styrene or other monomers, air-dried allyl functional groups, cationic curing of vinyl ethers or epoxides, condensation of isocyanates and thermal curing in the presence of acid catalysts. It is also possible cure under the action of the combination of UV radiation and electron beam. Combined curing mechanisms may be provided, for example, by mixing the substances with functional groups of the two types in a single structure, or mixing various substances with functional groups of the same type. This system analyzes Peeter in "Overview of Dual-Cure and Hybrid-Cure Systems in Radiation Curing", in Radiation Curing in Polymer Science and Technology: Volume III, Polymer Mechanisms edited by Fouassier and Rabek, Elsevier Applied Science, NY, Chapter 6, 177-217 (1993).

Among the materials capable of curing by radiation, it is preferable materials, cured by free-radical mechanism. Examples of such materials include, without limiting it, a mono - or multi-functional acrylates (i.e., the acrylates and methacrylates), calironia epoxides, calironia polyesters, calironia aroma is practical or aliphatic urethanes, calironia acrylates, calironia silicones, etc. and their mixtures or compounds. They can be monomers or oligomers (i.e. polymers with low molecular weight, typically containing from 2 to 100 monomer units, usually from 2 to 20 monomer units) with different molecular weights (e.g., with an average molecular weight of from 100 to 2000). Among the preferred starting substances coatings are calironia epoxides, calironia polyesters calironia aromatic or aliphatic urethanes and calironia acrylates. Calironia aromatic or aliphatic urethanes are among the preferred starting substances and calironia aliphatic urethanes are among the most preferred starting materials.

System, cured by free-radical mechanism, often contain oligomers and/or polymers (often called film-forming agents), which create a supporting frame formed of the cured material, and reactive monomers (often called reactive diluents), intended to regulate the viscosity of the curable compound. Although usually binders are oligomeric or polymeric substances, some Monomeric substances are also capable of forming films. Typically, such systems shall neither require the use of UV or electron radiation. System, cured by ultraviolet radiation, usually contain photoinitiator. To reduce the viscosity of the system can be used water or organic solvent (i.e. a solvent not participating in the reaction), although this usually requires heat treatment to remove solvent. Therefore, the preferred source of the substance coating does not contain water or organic solvents. In other words, they preferably are 100% solid compositions.

In the preferred composition of the original substance coating according to the present invention includes a film-forming substance and participating in the reaction diluent. Such participates in the reaction diluent includes at least one mono - or multi-functional Monomeric substance. Here, the term "mono-functional" means that the substance contains a single double bond carbon-carbon, and "multi-functional" - it contains more than one double bond in the carbon-carbon or other reactive group capable of participating in crosslinking by condensation. Among the resins with double bonds of carbon-carbon and other reactive groups include, for example, methacryloxypropyltrimethoxysilane, isocyanatomethyl and isobutoxyethene. Suitable uchastvuya and the reaction diluents are the same substances typically used to control viscosity of systems capable of curing under the influence of radiation. They are preferably acrylates, although it is possible the use of such non-acrylate compounds as N-vinylpyrrolidone, lemon and symonenaked if these monomers are not saturated with ethylene, which ensures their reactivity. The composition of film-forming material includes at least one substance capable of curing under the influence of radiation, such as mono - or multi-functional compound that is typically used in systems, radiation-curable, although it is also possible the use of thermoplastic polymers. Such thermoplastic polymers can be "self-reactive" (i.e. capable of forming internal cross connection) and can join or not to react with the reactive diluent.

Preferably, the starting material contains at least one monofunctional monomer component and at least one multifunctional oligomeric component. More preferably, such initial substance contained in at least one monofunctional Monomeric acrylate with a molecular weight not exceeding about 1000 (preferably about 100... 1000), and at least one of multifunctionals the second oligomeric atilirovanie urethane has a molecular weight of not less than about 500, preferably from about 500 to about 7,000, and more preferably from about 1000 to about 2000.

Monofunctional monomers usually have the ability to reduce the viscosity of the compound and to provide a more rapid penetration into the underlying layer. Multifunctional monomers and oligomers (e.g., diacrylate and triacrylate) usually provide the formation of a larger number of cross-links and more durable connection between the layers and within each layer. Moreover, depending on its structure, multifunctional monomers and oligomers can impart flexibility or rigidity. Calironia oligomers, preferably oligomers acelerando urethane, give the flooring such desirable properties as impact strength, hardness and flexibility.

Examples of suitable monofunctional monomers include, without limiting it to, acrylate, methacrylate, isooctadecyl, ethoxylated phenolicresin, isobutylacetate, 2-hexyl acrylate, 2-phenoxyethylacrylate, 2-(ethoxyethoxy)acrylate, caprolactone, tetrahydrofurfurylamine (THF-acrylate), etilenglikolevye and methoxytrimethylsilane. Examples of suitable multifunctional monomers include, without limiting it, triethylenemelamine, pentaerythritoltetranitrate, glycerol is remediability, glyceroltrinitrate, glycerylmonostearate, trimethylpentanediol, trimethylpropane, tetramethylethylenediamine, 1,6-hexanediamine, 1,4-potentialities, tripropyleneglycol, etilenglikolevykh, etilenglikolevye, polietilenglikolmonostearat, pentaerythritoltetranitrate, pentaerythritoltetranitrate and 1,6-hexanediamine. Other mono - and multifunctional monomers include vinyl acetate, N-vinylformamide, N-vinylcaprolactam, ethoxyacetylene etc. These monomers are commercially available under the trademarks EBECRIL company UCB Radcure Inc., Smirna, GA, PHOTOMER company Henkel Corp., Hoboken, NJ, SARTOMER company Sartomer Co., West Chester, PA. Symonenaked supplies Aldrich Chemical Co., Milwaukee, Wl. N-vinylpyrrolidone supplies Kodak, Rochester, NY.

Examples of suitable accelerandi oligomers include, without limiting it, calironia epoxides, calironia polyesters, calironia aromatic or aliphatic urethanes, calironia silicones, calironia ethers, vinylacetate, calironia oil and calironia acrylates. Which one is preferable calironia aromatic or aliphatic urethanes, and calironia aliphatic urethanes are most preferred because they are more flexible and more resistant to the weather factor is. Examples of some accelerandi aliphatic urethanes (i.e. aliphatic urethaneacrylate) includes compounds commercially available under the trade names PHOTOMER 6010 (molecular weight 1500) company Henkel Corp., Hoboken, NJ, EBECRIL 8401 (molecular weight 1000) and EBECRIL 8402 (molecular weight 1000, urethaneacrylate) company UCB Radcure Inc., Smirna, GA; and delivered by the company Sartomer Co., West Chester, PA, S-9635, S-9645 and S-9655 containing 25% of isobutylacetate (by weight), S-966-B80, containing 20% (by weight) of hexanenitrile and S-966-A80, containing 20% (by weight) of tripropyleneglycol.

To increase the solubility of the reactive resins (for example, accelerandi oligomers) and/or thermoplastic polymers of high molecular weight in the starting material of the coating may include various solvents other than the above dilution of the monomers. Such solvents are called nonreactive diluents or nonreactive monomers, because they do not participate significantly in the polymerization or crosslinking with the resin of the original substance, for example, in the curing conditions in accordance with the methods according to the present invention. Moreover, these solvents usually removed by heating, although their complete removal is not always necessary. Among the suitable solvents WMO is it different ketone solvents, tetrahydrofuran, xylan and the like. However, the preferred alternative is a 100% solids composition of the original substance in accordance with the above definition.

If desirable, an initial substances can be included dyes (i.e. pigments or paints). Examples of acceptable colorants include titanium dioxide, phthalocyanine blue, black carbon, white basic lead carbonate, zinc oxide, zinc sulfide, antimony oxide, zirconium oxide, sulfochromate lead, bismuth Vanadate, molybdate and bismuth, as well as other pigments, in particular, opaque pigments described in U.S. patent No. 5.706.562 (Coderre) and organic pigments described in U.S. patent No. 5.706.133 (Orensteen). The dye can be added in an amount to provide the desired coloration, and can be introduced into the starting material in many different ways.

Preferably the composition of the original substance is reactive diluent in an amount of from about 5% to about 25% of the total mass of the initial substances. The amount of film-forming substance and the additional dye in the original substance depends on the desired opacity, flexibility, viscosity, etc. Preferably, the film-forming substance is from about 25% to about 95% (by weight), and the dye is not more than about 50% (by weight) from fully the mass of the original substance.

In the original substance according to the present invention, curable by ultraviolet radiation, as a rule, includes photoinitiator. In a number of illustrative examples of the photopolymerization initiators (i.e. photoinitiators) are not limited to the following, organic peroxides, azo-compounds, quinones, benzophenone, nitroso compounds, acryl halide compounds, hydrazone, mercapto-compounds, prelievi connection, triarylamines, bisimides, globalcitizen, benzonatate, butylketone, thioxanthone and derivatives of acetophenone. The specific examples include benzyl, methyl o-benzoate, benzoin, benzonatate, tertiary amine benzophenone, such acetophenone as 2,2-diethoxyacetophenone, benzylmercaptan, 1-hydroxycyclohexyl, 2-hydroxy-2-methylpropan-1-it, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-it, 2-benzyl-2-N,N-dimethylamino-1-(4-morpholinyl)-1-butane, 2,4,6-trimethylbenzenesulfonamide, 2-methyl-1-4(methylthio)phenyl-2-morpholine-1-propanone, bis(2,6-dimethoxybenzoyl)(2,4,4-trimethylpentyl)phosphine oxide, etc. In the number of such photoinitiators are commercially available under the trademarks DAROCUR and IRGACURE company Ciba-Geigy Corp., Ardsley, NY. As a rule, photoinitiator is added in amounts necessary to achieve the desired reaction rate. Preferably he COI the box is used in amounts from about 0.01 percent by weight to about 5%, and more preferably, from about 0.1% to about 1% of the total mass of the original substance.

Other components that may be included in the composition of the source materials are filters, dampers foam, amplifiers adhesion, "rasslaivatei" (for example, such a tool to increase yield, as polydimethylsiloxane), humidifiers, tools, increase lubricity, stabilizers, including substances added to improve resistance to environmental exposure (for example, substances that increase the temperature resistance, visible or ultraviolet radiation), plasticizers, substances that improve adhesion, etc. Such components can participate or not participate in the reactions, but they generally do not participate in the reactions. Examples of participating in reactions plasticizers can serve as commercially available under the trademarks SARBOX SB-600 and SB-510E35T company Sartomer Co. Typically, such additives are introduced in amounts necessary to obtain the desired characteristics. Preferably they are added in amounts from about 0.01 percent by weight to about 5%, and more preferably, from about 0.1% to about 1% of the total mass of the original substance.

In accordance with the present invention can be applied to any method of applying the parent substance of the coating. The choice of the method of application depends on the viscosity of the similar substances, the desired thickness of the coating, the speed of coating, etc. are Acceptable methods of application were discussed above. As a rule, use the thickness of the base layer is from about 10 microns to about 250 microns.

After applying the initial substance on the underlying layer, it is preferably exposed to an energy source to initiate curing. Examples of acceptable and preferred energy sources are thermal energy and the radiation energy. The energy required depends on many factors, including the chemistry of the resin, the amount of the put of source materials, the number and nature of the additives, especially the added pigment. For thermal energy characteristic temperature from about 30°C to about 100°C. the exposure Time may vary from about 5 minutes to over 24 hours, and large durations correspond to lower temperatures.

Among the sources of radiant energy suitable for use in accordance with the present invention, includes e-rays, ultraviolet radiation, visible light, and combinations thereof. E-beam, also known as "ionizing radiation" may be used when the energy levels from about 0.1 Mrad to about 10 Mrad, preferably from about 3 Mrad to about 8 Mrad, and more PR is doctitle, from about 5 Mrad to about 6 Mrad at an accelerating voltage of from about 75 kV to about 5 MB, preferably at an accelerating voltage of approximately 100 kV to about 300 kV. Under ultraviolet radiation refers to radiation (not bearing particles) with a wavelength in the range from about 200 nanometers to about 400 nanometers. It is preferable to use ultraviolet radiation had a density of 118...236 watts/cm2. Under visible light refers to light (not bearing particles) with a wavelength in the range from about 400 nanometers to about 800 nanometers. When using radiant energy of a particle of some pigments and/or other additives can absorb this energy, preventing polymerization of the resin included in the composition of the educt. If this phenomenon occurs, it is possible to use a higher dose and/or increase the number of photoinitiator to the level of providing compensation for a specified radiation absorption. Similarly, you may need to increase the accelerating voltage of the electron beam to increase the penetrating ability of ionizing radiation.

Dyes

Suitable coloring agents are the same substances that are used in various printing processes for painting surface areas, for example, a color different from ejecuta (matte color) to printed information could be distinct in one way or another. Typically, these dyes create visible to the naked eye image, consisting of selected alphanumeric characters or other symbols, for example, bar codes, logos, etc. of the desired color. However, if desired, information may be readable by other means (for example, the perceived device infrared image). Examples of such pigments are substances commonly used in non-contact printers (for example, toners for laser printers), as well as during contact printing (for example, ink containing rubber band printers with thermal mass transfer). Typically, for each printing process for the formation of printed images require special dye. Some dyes have been specifically designed to avoid the need for a spray starch to eliminate otmerivanija sheet when printing or for the prevention of air pollution-volatile solvent ink roll when printing. There are dyes that mimic metallic luster, create magnetized image, readable only with the help of electronic equipment, images, resistant to alcohol and erase the label of alcoholic beverages, the mouth of ichiye to alkali for packing soap, fluorescent, with increased brightness to increase the attractiveness of the image. There are ink designed specifically for screen printing, letterpress, gravure and flexographic printing. Many of these dyes require curing by radiation (for example, inks fastened ultraviolet or ionizing radiation), which were created to address problems of environmental pollution associated with sputtered or dissolved materials. Coloring materials, curable by ultraviolet radiation, typically contain liquid prepolymers (oligomers and/or monomers and initiators, which under the influence of intense ultraviolet radiation to form free radicals, instantly polimerizuet solvent in dry dense thermoplastic resin. There are coloring materials, curable with ionizing radiation, but they do not contain initiators.

Dyes are often designed for certain printing processes, in which they will be used to create images. In General, suitable for use according to the present invention are dyes containing a dye (e.g., pigment or dye), a carrier-based resin (i.e. binder), in which is dissolved or dispersed dye, and the other is e possible additives to enhance drying and/or to give the necessary performance. Some of the components of dyes are used in various printing processes, can belong to the same family of substances, but their individual properties may need to be modified in accordance with the characteristics of used printing technology. For example, the resin from the family of polyesters can be used as a binder for screen printing, Electrophotography, thermal transfer, etc. but to each their molecular weight, degree of cross linking and the particular monomers can be selected are different.

To ensure good adhesion to surfaces with improved adhesion of the marking of products spasmo the present invention, in particular, to materials, utverzhdennym under the action of radiation, binder coloring substance preferably contains reactive components, i.e. substances capable of forming cross-links and/or by polymerization of a wide range of mechanisms (e.g. oxidative curing, condensation, solidification under the influence of moisture, radiation or thermal curing of free-radical systems, and so on). More preferably, binding the coloring matter contained polymer selected from the group comprising complex polyester, vinyl, polyolefin, polyvinylacetal, alkyl - or aryl-samewe the hydrated acrylate or methacrylate, a copolymer of ethylene or propylene with acrylic acid, methacrylic acid or vinyl acetate, or a combination of these substances. As an example, in table 2 of the section "Examples" presents a wide variety of types of coloring substances, are applied with different types of printers.

Colorants and additives for different types of dyes and printing devices may be different, as is well known familiar with this area. Many of acceptable dyes and additives were mentioned above when discussing the chemistry of a surface with improved adhesion.

Printers

Described here colorants can be used in many types of printing devices, both contact and non-contact, preferably digital printing devices, to create images on surfaces with improved adhesion, particularly on special substrates for printing, and is particularly described herein radiation hardened coatings. It can be electrostatic, electrophotographic device using the deposition ions, magnetic tape, inkjet (ink) device with mass transfer and device bitmap, deep, high and offset printing. Many processes used in digital printing (e.g., electrostatic, electrophotographic the Kie, magnetic tape and inkjet devices and devices with mass transfer or use of deposition ions), in which information about the image is in digital form. Such processes are used mainly for short runs and for urgent printing on different orders or personalized information, such as addresses, codes, etc.

Below is a brief description of some of the processes of printing, suitable for use within the methods according to the present invention. More complete information can be found in the standard guidelines for printing. Examples of such guidelines are the Principles of Non Impact Printing. J.L.Johnson, Palatine Press (1986); Understanding Digital Color. Phil Green, Graphic Arts Technical Foundation (1995), pp. 293-310; and Pocket Pal, A Graphic Production Handbook, published M.Bruno, International Paper Co., 16thedition (1995), pp. 126-150.

Electrostatic printing comprises the step of creating the image by applying an electric charge directly on print-ready surface and step staining using liquid toner. Then follows the stage of fixing the toner with heat and pressure. There is a large selection of printers using this method of printing with a width of up to 52 inches (up to 132 cm). They are used for printing architectural drawings, posters, etc. Devices electrophotographic printing (including laser the Yu printing and xerography) is similar to high-speed imaging systems. In the electrophotographic system includes, for example, electrostatic photoconductor charged by corona discharge under a laser, modulated signal produced by the digital image processing system based on the software product, PostScript, and device migration painted image from the photoconductor to the substrate. Such systems are used for printing variable information in one color or in specialized systems) multiple not blending colors with a speed of up to 300 feet (almost 100 m) per minute. Market color printing are also slower system for four-color printing variable and operational information.

The printing method of the electrostatic deposition of ions, often called the creation of the image of the electronic beam (EB), consists of four simple steps: (1) a loaded image is created by a beam of charged particles (electrons)that flows from the cartridge to the heated surface of the rotating drum from a very solid anodized aluminum, (2) one-component magnetic toner is attracted to the surface as the drum rotates, (3) colored image is transferred to the substrate and fixed on it by pressure, (4) the excess toner removed from the drum. Now he is ready to create a new image. The new system uses the light is using the latest dye capable of creating high-quality images with smooth transitions of the four colors. Magnetography same way EBI with the difference that it uses the magnetic drum, the surface of which is under computer control is created magnetized alternating image, and one-component magnetic toner. Its main advantage is the ease of creating images using digital data.

Inkjet printing is mainly used for printing variable information such as codes and addresses prepared on the computer, emails, forms of betting on the tote and in other cases requiring direct indications of personal email addresses. There are many types of inkjet printers: continuous after that splashed on command, bubble-jet, single jet and multi-jet. The image is created using digital methods using water-soluble ink. Inkjet printers form droplets of ink or the extrusion jet through the nozzle pressure, or throwing out individual drops on the commands depend on the generated image. Printers, producing a drop on command, do this either heat (evaporation of ink)or piezoelectric (phase change) by.

Device with thermal mass transfer using computer-generated digital texts and images to control thermal printhead that generates n the tapes with dyes [doner - sic] of the molten ink dots, which are then transferred to the substrate. Currently used systems have built-in computers and made containing up to 25% of the variable information completely ready labels and other printed products, in four colors, laminated and cut rotary or flat cutter.

Bitmap printing is a unique process, suitable for printing small runs on virtually any surface. They can be printed graphics and tone of the image.

Sometimes bitmap printing is performed manually using very simple equipment, consisting of a table, a frame with a raster and a rubber roller.

However, in most commercial applications, raster printing is performed by mechanized devices. In the process of printing inked a raster with a pattern corresponding to the desired image, closely pressed to the substrate, and a rubber roller through the open areas of the fabric raster presses the ink on the substrate. Then the substrate with the printed image is dried to remove solvent from the ink, and this completes the process.

The device gravure printing comprises printing cylinder, clamping cylinder and ink system. Ink (dye) is served on a printing cylinder blown air is m roller or spray moreover, the excess ink is removed by the squeegee blade and returns to the inking unit. The presser cylinder covered with a rubber composition, holding ink surface on which should be made an imprint. Gravure printing is used in the manufacture of packaging materials, coatings for floors that do not allow compression Wallpaper, plastic laminates, etc.

In a family of devices for high print consists of three basic designs: flat printing machine, vertical roll ink machines and rotary printing machines. Many commercial works are carried out on machines, sheet fed, but most large-circulation publications (magazines, books, Newspapers) are printed on machines with roll feed. More detailed information about these types of printing devices can be found in the paper cited above guide Pocket Pal. A Graphic Production Handbook. Printing machines have three printing cylinder and the same ink and dampening systems. As the rotation of the printing cylinder he comes in contact first with the moisture, and then with a paint roller. The moisturizing roller wets printing cylinder, so that its surface form does not print areas, pushing the paint. Then, the ink image is transferred to a rubber cloth, and when the paper passes between the panel and prig who set aside by the Russian cylinder, it remains in print. Web offset machines capable of printing speeds of up to 3000 feet (1000 meters) per minute and used for printing Newspapers, magazines, stationery, computer letters, catalogs, trade by mail, gift packages, etc. for More detailed information about these types of printing devices can be found in the paper cited above guide Pocket Pal, A Graphic Production Handbook.

EXAMPLES

The goals and benefits of the present invention are illustrated in detail below by examples, but such a specific substance, their quantity, as well as other conditions and details in no way should be construed as limiting the present invention.

Preparation of materials

Preparation of the substrate for the printing of the acrylate-methacrylate copolymer.

The acrylate-methacrylate copolymer (3M SCOTCHLITE 880 Clear Coat company Minnesota Mining and Manufacturing Co., St. Paul, MN) was applied onto the surface of the reflective coating (SCOTCHLITE RRS 3750 company Minnesota Mining and Manufacturing Co., St. Paul, MN) use the accessories K-Coater (firm Testing Machines, Inc., Amitville, NY) and wire lath QC bar #2. Then the coating was 10 minutes, placed in a furnace with a temperature of 270°F (130° (C)to the thickness of the cured coating was about 1 mil (0.025 mm). This coating is made in table 1, as the coating 2.

Preparation of the substrate for printing from ethylenevinylacetate what about the copolymer.

Extruded film (1 mil) of resins, including Binel 3101 (containing acrylate ethylenevinylacetate copolymer DuPont Company, Wilmington, DE, floor 3, table 1); Chevron 1305 (ethylenevinylacetate copolymer firm Chevron Co., San Francisco, CA, floor 5, table 1); Elvax 260 (ethylenemethacrylic copolymer DuPont Company, Wilmington, DE, floor 4, table 1) were heated and pressure applied to the surface reflective coating (SCOTCHLITE RRS 3750 company Minnesota Mining and Manufacturing Co., St. Paul, MN) at a temperature of 325°F (about 165° (C) in the circumstances described in U.S. patent No. 4.664.966 (Bailey and others). These coatings can also be applied from a solution.

Preparation of the substrate for printing from sulfopolysaccharide with sellowii terminal groups.

Sulfopolysaccharide with sellowii terminal groups described in U.S. patent No. 5.756.633 was caused by using accessories K-Coater (firm Testing Machines, Inc., Amitville, NY) and wire lath QC bar #2 on the surface of the reflective coating (SCOTCHLITE RRS 3750 company Minnesota Mining and Manufacturing Co., St. Paul, MN). Then the coating was air-dried so that the thickness of the cured coating was about 1 mil (0.025 mm). This coating is made in table 1, as the floor 6.

Preparation of the substrate for printing UV Clear Coat.

Sublayer for printing (3M SCOTCHLITE 9200 series Clear coat (coating 8, table 1) and 9700 Toner (floor 7, table 1), (both of these substances set Auda company Minnesota Mining and Manufacturing Co., St. Paul, MN) were deposited on the surface of the reflective coating (SCOTCHLITE RRS 3750 company Minnesota Mining and Manufacturing Co., St. Paul, MN) use the accessories K-Coater (firm Testing Machines, Inc., Amitville, NY) and wire lath QC bar #4. Coated panels were solidified moving under mercury lamps, medium pressure with a speed of 27 feet (8 m) per minute up to a dose of radiation 0,324 j/cm2. The thickness of the dry coating each of the samples amounted to 0.9 mils (0,023 mm). Using other wire Reiki, you wish to get thinner and thicker coatings.

The control coating in table 1 represents a thermally utverjdenie coating based esters, which is the top layer in 3M SCOTCHLITE Security Validation Sheeting 5330, commercially supplied by company Minnesota Mining and Manufacturing Co., St. Paul, MN.

Floor 1 in table 1 represents a thermally utverjdenie transparent coating of Akzo Nobel Inks, Inc., Arnhem, The Netherlands, commercially available under the trade mark WERNEKE ARCXX0013. This material was deposited on the surface of the reflective coating (SCOTCHLITE RRS 3750 company Minnesota Mining and Manufacturing Co., St. Paul, MN) using a flexographic press and kiln dried to obtain a dry coating thickness of 0.3 mil (0,0008 mm).

Test procedures:

Check adhesion.

Sheets of reflective material coated and printed the image is pasted on a flat aluminum panel with a conversion coating company The Q-Panel Co., 26200 First St, Cleveland, HE (the material for rain gutters) with its own adhesive layer of the retroreflective material. The panel had a size 11×2.75 inches (x cm). A piece of tape brand 3M 610 (pressure-sensitive adhesive tape company Minnesota Mining and Manufacturing Co., St. Paul, MN) clung to the image (or only to the sublayer for printing) by the force of the thumb.

After otkleivanie tape qualitatively assessed the quantity of the removed material. Score 10 points means that the material is practically not removed, whereas a score of 0 points means that was removed a significant portion of the test material (substrate for printing or coloring matter). Although quantitative measurements of image density were taken, for example, that a score of 7 points (depending on the thickness of the test coverage) in General corresponds to 70% of the surviving material.

The test for resistance to abrasion.

Abrasion resistance in the wet state was tested by a modified method of the Federal Standard Test Methods (ASTM) 141a, Method 6142, Gardner Laboratory Bulletin WG 2000) using devices Gardner Model M-105 and Gardner Straight Line Washability and Abrasion Tester No. 1364.

Samples for testing were prepared by stickers two samples retroreflective material coated and printed the image on a flat aluminum the second panel with the conversion coating company The Q-Panel Co., 26200 First St, Cleveland, HE (the material for rain gutters). The panel was about the size h,75 inches. After applying the samples to the panel, they tightly pricecialis to it with a small rubber roller for paper (with a diameter of approximately 1.5 inches).

After soaking the brush from Chinese pig bristles in warm water (approximately 100-120°F (45-50° (C)within 30 minutes, it was removed excess water. Then brush within 5 minutes was treated with 0.5%solution of detergent ("Dreft"). Brush from Chinese pig bristles were placed in the brush holder test apparatus. The test panel was installed in the test device. The test instrument was slightly modified so that it could set the panel size 11×2.75 inches. The test cycle consisted of 1000 cycles of the brush. During the test panel with a frequency of about 12 times per minute was administered with 0.5%solution of detergent ("Dreft") in the title column (just in such quantity that the panel was still wet). Then the test panel was opolaskivatel and dried.

The number of the deleted material was evaluated qualitatively. Score 10 points means that the material is practically not removed, whereas the assessment Of points means that was removed a significant portion of the test material (substrate for printing or coloring matter). Although to icestone measure the density of the image was not carried out, taken, for example, that the evaluation of the resistance to abrasion of 7 points in total corresponds to 70% of the surviving material.

Tested for weather resistance.

Resistance to weather conditions was estimated by the method of ASTM G53. The samples (leaves retroreflective material coated and printed) were prepared and tested according to the procedure of ASTM G53 (1996) (with ultraviolet fluorescent lamps of the type "B") in the cycle exposure (4 hours under ultraviolet radiation at the temperature of the black surface 60°C), followed by a cycle of condensation (4 hours at the temperature of the black surface 50°).

The evaluation of the samples was performed by comparing the tested sample with the same sample not subjected to testing, and served as a control. Samples were evaluated, for example, by changing the surface properties as gloss (e.g., Shine sublayer for printing), adhesion (for example, adhesion of the coloring matter), fading (e.g., fading of the coloring matter) compared with the corresponding control sample. Used scale 0...10 points where 10 means the absence of changes, and a score of 0 means that there have been significant changes (for example, disappeared dye or sample has been detaching the I).

Tests for resistance to solvents.

Tests for resistance to solvents and detergents was performed by the method described below. The samples were prepared by stickers, two sheets of reflective material coated and printed the image on a flat aluminum panel with a conversion coating company The Q-Panel Co., 26200 First St, Cleveland, HE (the material for rain gutters). The panel had a size 11×2.75 inches. After applying the samples to the panel, they tightly pricecialis to it with a small rubber roller for paper (with a diameter of approximately 1.5 inches). As a test solvents were used: methyl alcohol, mineral spirits, kerosene, naphtha VM&P and gasoline (standard, no lead). (Note: solvents that can damage the painting or varnishing of vehicles should not be used as a test.) As a test detergents were used: detergent "409", liquid for washing Windows, ammonia, liquid to remove tar and traces of insects (distillate oil or mineral spirits).

Mounted on the stem end of the cotton swab ("Q-tip") specialsa appropriate solvent or test detergent. The pilot was holding the pad at an angle of 45 degrees with respect to the subject product and go active with diaepam hand force of about 40 g did 10 cycles of reciprocating motion (one cycle consists of moving across the sample and back) wet swab on the image on its surface. On the second sample, the test was performed 25 such cycles.

The number of the deleted material was evaluated qualitatively. Score 10 points means that the material is practically not removed, whereas a score of 0 points means that was removed a significant portion of the test material (substrate for printing or coloring matter). Although quantitative measurements of image density were taken, for example, that the evaluation of the resistance to solvents 7 points, in General, corresponds to 70% of the surviving material.

Although it is not specifically shown, each of the samples was assessed by 10 points after testing tool "409", liquid for washing Windows, liquid ammonia, liquid for removal of tar and traces of insects, methyl alcohol, and mineral spirits. The test results kerosene and naphtha VM&P in General similar to that shown in table 1 the results of the tests with gasoline, but more favorable.

Presented in the table cover 1, 2 and 3 were designed as a protective coating, which is resistant to solvents and cleaning agents that caused the image to allow cleaning. Therefore, coatings 1, 2 and 3 (they are all thermoplastic coatings), although well-suited for printing, are not preferred because of high enough resistance to gasoline.

Tests if agnosti for printing.

Suitability for printing samples of retroreflective materials with various described above sublayers for printing was tested with the following printers. Small sheets of reflective material coated glued (using the adhesive layer of retroreflective material) on a sheet of paper that has passed through the printer in accordance with the attached instructions. In the printer sent them the image (page duplicate texts prepared by using a text editor of Microsoft Word™).

After printing, the samples were subjected to the above tests.

In order to check the suitability for printing samples listed in table 1, were used printer HP LaserJet III at Hewlett Packard Company, Palo Alto, CA with cartridge toner A (styren-acrylic resin).

The data presented in table 2, obtained using the printer:

- HP Laser Jet III at Hewlett Packard Company, Palo Alto, CA with cartridge toner A;

- HP Laser Jet III at Hewlett Packard Company, Palo Alto, CA with replaceable cartridge for toner A supplied by the company Laser Sharp, Inc., Hastings, MN as "toner Cartridge for MICR";

- Laser printer Minolta Pageworks 8L firm Minolta Corporation, Peripheral Products Division (PPD), Mahwah, NY, with the appropriate cartridge for the toner;

- Inkjet printer HP Model 2000 Hewlett Packard Company, Palo Alto, CA, with a corresponding CT is the ridge for ink;

- Inkjet printer solid ink Model Phaser III firm Tektronix Inc., Wilsonville, OR, with ink rod "part # 016-1123-00";

- Printer with thermal mass transfer Model 171 company Zebra Technologies Corp., Vernon Hills, IL with ribbon AD501 firm Advent Corp., Romeo, Ml.

- Tested with a high printing was carried out using a test set Quickpeek company Thwing-Albert Instrument Co., Philadelphia, PN;

- Tested with a bitmap printing was conducted using a standard set of equipment for screen printing with ink series 9700 3M brand Scotchlite™ in accordance with the instruction attached to the kit.

Cited here full disclosure of the patents, patent documents and publications are included for reference in their entirety as if each was incorporated individually. Various modifications and changes of the present invention, for obvious familiar with this area, do not constitute departures from the spirit and scope of the present invention. It should be understood that the present invention can not be considered limited given here illustrate examples of embodiments that such examples of embodiment given here for the sole purpose of illustration and that the scope of the present invention may be limited only by the following formula is th invention.

1. Marking a product consisting of a substrate that has not containing cellulose organic polymeric surface; cured radiation coating located on a specified does not contain a cellulose organic polymeric surface, and the coloring matter deposited on the specified utverjdenie radiation coating, characterized in that the substrate contains a light-reflecting layer, but such dye is not removed in significant ways from marking the product as a result of at least five cycles of wiping the specified coloring substance gasoline.

2. Marking article according to claim 1, characterized in that the reflective layer is part of the certification label.

3. Marking article according to claim 1, characterized in that the dye comprises a dye and a binder, with specified binder comprises a polymer selected from the group comprising polyester, vinyl, polyolefin, polyvinylacetal, alkyl - or aryl-substituted acrylate or methacrylate, a copolymer of ethylene or propylene with acrylic acid, methacrylic acid or vinyl acetate, and combinations thereof.

4. Marking article according to claim 1, characterized in that utverjdenie radiation coating obtained from a material capable of curing the electron beam.

5. Marcero the full product according to claim 1, characterized in that utverjdenie radiation coating obtained from a material capable of curing by ultraviolet radiation.

6. Marking article according to claim 5, characterized in that the curable by ultraviolet radiation material is an acrylate.

7. Marking article according to claim 6, characterized in that the acrylate is an aliphatic acrylourethane.

8. Marking article according to claim 1, characterized in that the dye is not removed substantially in the ten cycles of wiping the specified coloring substance gasoline.

9. Marking article according to claim 7, characterized in that the dye is not removed in significant ways in the twenty-five cycles of wiping the specified coloring substance gasoline.

10. Marking article according to claim 1, characterized in that the dye is not removed substantially in the 1000 cycles mechanical wiping of the specified coloring matter.

11. Marking article according to claim 1, characterized in that the dye is not removed substantially in the crushing force of the thumb to the specified kasashima substance, a pressure-sensitive adhesive tape and remove it.

12. Marking article according to claim 1, characterized in that utverjdenie radiation coating does not have alaysia significantly in the crushing force of the thumb to the specified otverzhdennom radiation-coated pressure-sensitive adhesive tape and remove it.

13. Marking article according to claim 1, characterized in that utverjdenie radiation coating is not removed in significant ways in the five cycles of wiping specified cured by radiation coverage gasoline.

14. Marking article according to claim 1, characterized in that utverjdenie radiation coating is not removed substantially in the 1000 cycles mechanical wiping specified cured by radiation coverage.

15. Marking article according to claim 1, characterized in that utverjdenie radiation coating is applied in the form of a drawing.

16. Marking article according to claim 1, characterized in that it has no protective coating on top of the coloring matter.

17. A method of manufacturing a marking products, consisting in the preparation of the substrate, consisting of not containing cellulose organic polymeric surface with a deposited utverzhdennym radiation coating, and applying coloring matter to the specified utverjdenie radiation coating, characterized in that the substrate contains a light reflective layer and for the application specified the coloring matter used technology selected from the group comprising a method of thermal mass transfer, electrostatic printing, printing, ion beam, magnetic tape printing, inkjet printing, letterpress, offset printing and CH is deep print.

18. The method according to p. 17, characterized in that the marking device does not have a protective coating on top of the coloring matter.

19. The method according to p. 17, characterized in that the dye comprises a dye and a binder, with specified binder being composed of a polymer selected from the group comprising polyester, vinyl, polyolefin, polyvinylacetal, alkyl - or aryl-substituted acrylate or methacrylate, a copolymer of ethylene or propylene with acrylic acid, methacrylic acid or vinyl acetate, and combinations thereof.

20. The method according to p. 17, characterized in that utverjdenie radiation coating obtained from a material capable of curing by ultraviolet radiation.

21. A method of manufacturing a marking products, consisting in the preparation of the substrate, consisting of not containing cellulose organic polymeric surface, and applying coloring matter to the specified does not contain a cellulose organic polymeric surface using a technology selected from the group comprising electrophotographic printing and gravure printing, characterized in that the substrate contains a light reflective layer and a specified dye is not removed in significant ways in the five cycles of wiping the specified coloring substance gasoline.

22. The method according to item 21, distinguish the different topics that marking a product does not have a protective coating on top of the coloring matter.

23. The method according to item 21, wherein the substrate containing bestselling organic surface contains utverjdenie radiation coating, which is applied to the coloring matter.

24. A method of manufacturing a marking products, consisting in the preparation of the substrate, consisting of not containing cellulose organic polymeric surface, and applying coloring matter to the specified does not contain a cellulose organic polymeric surface using a technology selected from the group comprising high printing and offset printing, characterized in that the substrate contains a light reflective layer, and that the specified marking the product does not have a protective coating on top of the coloring matter, such dye is not removed in significant ways in the five cycles of wiping the specified coloring substance gasoline.

25. The method according to paragraph 24, wherein the substrate containing bestselling organic surface contains utverjdenie radiation coating, which is applied to the coloring matter.

26. The method according A.25, characterized in that utverjdenie radiation coating obtained from a material capable of curing by ultraviolet radiation.

27. A method of manufacturing identification labels consists in preparing certification label that has not containing cellulose organic polymeric surface, and screen printing on specified does not contain a cellulose organic polymeric surface, wherein the surface contains light-reflecting layer, but also the fact that the marking device does not have a protective coating on top of the coloring matter, such dye is not removed in significant ways in the five cycles of wiping the specified coloring substance gasoline.

28. A method of manufacturing a marking products, consisting in the preparation of the substrate, consisting of not containing cellulose organic polymeric surface, on which there is utverjdenie radiation coating, and screen printing dye on the specified dry radiation coating, characterized in that the substrate contains a light reflective layer, and that the specified marking the product does not have a protective coating on top of the coloring matter, such dye is not removed in significant ways in the five cycles of wiping the specified coloring substance gasoline.



 

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